Seawater contribution to polymetallic Ni–Mo–PGE–Au mineralization in Early Cambrian black shales of South China: Evidence from Mo isotope,PGE, trace element,and REE geochemistry

The Early Cambrian black shale sequence of the Niutitang Formation in South China hosts a synsedimentary, organic carbon-rich, polymetallic sulfide layer with extreme metal concentrations, locally mined as polymetallic Ni–Mo–PGE–Au ore. In combination with previously reported data, we present Mo isotope, platinum-group element (PGE), and trace and rare-earth element (REE) data for the polymetallic sulfide ores and host black shales from four mine sites (Dazhuliushui and Maluhe in Guizhou Province, and Sancha and Cili in Hunan Province, respectively), several hundred kilometers apart. The polymetallic sulfide ores have consistently heavy δ^98/95Mo values of 0.94 to 1.38‰ (avg. 1.13 ± 0.14‰, 1σ, n = 11), and the host black shale and phosphorite have slightly more variable δ^98/95Mo values of 0.81‰ to 1.70‰ (n = 14). This latter variation is due to variable paleoenvironmental conditions from suboxic to euxinic, and partly closed-system fractionation in isolated marine sedimentary basins. Both the polymetallic sulfides and host black shales show PGE distribution patterns similar to that of present-day seawater, but different from those of ancient submarine-hydrothermal deposits and modern submarine hydrothermal fluids. The polymetallic sulfide bed has a generally consistent metal enrichment by a factor of 10⁷ compared to present-day seawater. PAAS-normalized REE + Y patterns of the polymetallic sulfide bed are characterized by a remarkably positive Y anomaly, consistent with an origin of the REE predominantly from seawater. Small positive Eu anomalies in some of the sulfide ores could reflect minor hydrothermal components involved. The Mo isotope, PGE, and trace and rare-earth element geochemical data suggest that metals in the polymetallic Ni–Mo–PGE–Au sulfide ore layer were scavenged mostly from Early Cambrian seawater, by both in-situ precipitation and local re-deposition of sulfide clasts.     

塔里木盆地中寒武统泥晶白云岩红层的地球化学特征与成因探讨

塔里木盆地西部克拉通台地区寒武系中寒武统发育大量泥晶白云岩红层。钻孔岩芯观察及岩石学分析表明,该白云岩以岩芯呈暗红色、显微镜下呈泥粉晶结构、并伴随有纤状石膏假晶与陆源石英碎屑为主要特征,指示了该白云岩形成于潮上带蒸发环境。地球化学分析结果表明,该白云岩具有固有属性的CaO％,MgO％含量正相关特征, 因此,塔里木盆地中寒武统泥晶白云岩红层属于典型的潮上带Sabkha型沉积的“原白云石”。泥晶白云岩红层U,Mo含量亏损,指示了该白云岩形成于氧化环境,与色泽较红相一致;稀土元素特征上,该泥晶白云岩红层稀土元素配分模式呈右倾特征,但是在陆源碎屑的影响下,常出现中稀土元素富集的“帽”型特征;碳氧同位素分析表明,泥晶白云岩红层碳同位素变化没有规律性,多数δ18OPDB值变化在-7‰~-4.4‰之间,与潮上带蒸发沉积的Sabkha特征一致;英买7井白云岩红层δ18OPDB值较低（＜-10‰）,可能为成岩作用过程中热液改造的结果;由于泥质矿物的存在,潮上带白云岩87Sr/86Sr比值一般比同期海水值偏高。     

Carbon Isotope Features of the Sugetbrak Section in the Aksu?Wushi Area, Northwest China: Implications for the Precambrian/Cambrian Stratigraphic Correlations

The upper Qigeblaq Formation （Fm） dolostones and the Yurtus Fm phosphatic cherts, black shales, limestones, and dolostones are widely distributed in the Precambrian/Cambrian transitional succession of the Aksu-Wushi area. Negative δ13C excursion above the Yurtus Fm/ Qigeblaq Fm boundary was determined in this study. The pronounced negative carbon isotope excursion occurs in the phosphatic chert layers at the bottom of the Cambrian Yurtus Fm, below which the first appearance of the Asteridium- Heh＇osphaeridium-Comasphaeridium （AHC） acritarch assemblage zone. The δ13C curve of the lower part of the Yurtus Fm in the Aksu-Wushi area was found to be correlated with the early Cambrian δ13C curves of the Zhujiaqing Fm （Daibu Member）, the lower part of the Yanjiahe Fm on the Yangtze Platform in China, the lower Tal Fm in India, the Sukharikha Fm in Siberia, and the upper part of the Tsagaan Oloom Fm in Mongolia through biostigraphy. The lower part of the Yurtus Fm in the Tarim Basin is at the Nemakit-Daldynian stage, and the Precambrian/Cambrian boundary of the Aksu-Wushi area may be located in the phosphatic chert unit which just below the first appearance AHC acritarch assemblage zone. The negative δ13C excursion （N1） across the Precambrian/Cambrian boundary in the studied section may have resulted from oceanic overturning and sea level rise.     

Isotopic-geochemical features of rocks of the Middle-Upper Cambrian Verkhnyaya Lena formation in the Siberian Craton

Isotopic compositions of carbon and oxygen in carbonates and sulfur in sulfates of the Verkhnyaya Lena Formation (ε₂–ε₃), which terminates the Cambrian section of the Irkutsk Amphitheater of the Siberian Craton, are studied. Sulfates of the Verkhnyaya Lena Formation are marked by unusually low δ³⁴S values (4.6–12.0‰) relative to sulfates of the underlying Angara Formation. This is likely caused by variations in the facies-paleogeographic sedimentation at the transition of the Angara and Verkhnyaya Lena formations, as well as associated variations in the water and salt alimentation budget in sedimentation basins, due to their isolation from open sea and intensification of the continental and underground discharge. The δ¹⁸O(PDB) value in carbonates decreases from ?4.4‰ at bottom to ?10.4‰ at top, reflecting variation in postsedimentary transformations and probable continuous freshening of sedimentation basin. Isotopic composition of carbon in most samples shows normal marine δ¹³C values (0 ± 1‰). Only in some samples, does the δ¹³C value increase up to ?3.8 and 2.2‰ due to specific features of postsedimentary processes. The Rb-Sr systems of the clayey component of marls from the 500-m-thick section of the Angara Formation and bottom of the Verkhnyaya Lena Formation record an age of 512 ± 10 Ma, which is close to the assumed stratigraphic age of the Verkhnyaya Lena Formation. The ⁸⁷Sr/⁸⁶Sr initial ratio is 0.7082 ± 0.0004.     

Redox history of the Three Gorges region during the Ediacaran and Early Cambrian as indicated by the Fe isotope

The Ediacaran-Cambrian transition is characterized by numerous events such as the emergence of large multi-cellular metazoans and surface environmental disturbances.Based on geological evidence,it has been proposed that this transition coincided with the increase in the atmospheric oxygen level that was key to the evolution of life.Even though ancient redox conditions can be inferred from the composition of sedimentary iron mineral species,this method is not necessarily applicable to all rocks.In the Earth system,the cycling of iron is of considerable interest owing to its sensitivity to redox conditions.Information regarding the paleo-oceanic iron cycle is revealed in the iron isotopic composition of ironbearing minerals.Unfortunately,only limited iron isotopic data exists for Ediacaran-to Cambrianperiod oceans.To circumvent this deficiency,we drilled a fossiliferous Ediacaran to Early Cambrian sedimentary succession in the Three Gorges region,South China.We analyzed the iron isotope ratios(δ~(56/54)Fe)of pyrite grains in the drill cores using laser ablation multi collector inductively coupled plasma mass spectrometry.The results demonstrate large variations inδ~(56/54)Fe,from-1.6 to 1.6‰,and positive iron isotope ratios are observed in many successions.The presence of positiveδ~(56/54)Fe in pyrite indicates that the ferrous iron in the seawater was partially oxidized,suggesting that seawater at Three Gorges was ferruginous during the Ediacaran and Early Cambrian periods.However,aggregated pyrite grains in organic carbon-rich black shales at Member 4 of the Doushantuo Formation and the base of the Shuijingtuo Formation yield near-zeroδ~(56/54)Fe values;this suggests that the ocean was transiently dominated by sulfidic conditions during these periods.Notably negativeδ~(56/54)Fe values,lower than-1‰,can be interpreted as a signature of DIR.The DIR also might contribute in part to the re-mineralization of organic matter during the largest negative carbon isotope anomaly in the Ediacaran.     

Geology,geochemistry and genesis of the Qianfanling quartz-vein Mo deposit in Songxian County,Western Henan Province,China

The Qianfanling Mo deposit, located in Songxian County, western Henan province, China, is one of the newly discovered quartz-vein type Mo deposits in the East Qinling–Dabie orogenic belt. The deposit consists of molybdenite in quartz veins and disseminated molybdenite in the wall rocks. The alteration types of the wall rocks include silicification, K-feldspar alteration, pyritization, carbonatization, sericitization, epidotization and chloritization. On the basis of field evidence and petrographic analysis, three stages of hydrothermal mineralization could be distinguished: (1) pyrite–barite–quartz stage; (2) molybdenite–quartz stage; (3) quartz–calcite stage.Two types of fluid inclusions, including CO₂-bearing fluid inclusions and water-rich fluid inclusions, have been recognized in quartz. Homogenization temperatures of fluid inclusions vary from 133 °C to 397 °C. Salinity ranges from 1.57 to 31.61 wt.% NaCl eq. There are a large number of daughter mineral-CO₂-bearing inclusions, which is the result of fluid immiscibility. The ore-forming fluids are medium–high temperature, low to moderate salinity H₂O–NaCl–CO₂ system. The δ³⁴S values of pyrite, molybdenite, and barite range from − 9.3‰ to − 7.3‰, − 9.7‰ to − 7.3‰ and 5.9‰ to 6.8‰, respectively. The δ¹⁸O values of quartz range from 9.8‰ to 11.1‰, with corresponding δ¹⁸O_fluid values of 1.3‰ to 4.3‰, and δ¹⁸D values of fluid inclusions of between − 81‰ and − 64‰. The δ¹³C_V-PDB values of fluid inclusions in quartz and calcite have ranges of − 6.7‰ to − 2.9‰ and − 5.7‰ to − 1.8‰, respectively. Sulfur, hydrogen, oxygen and carbon isotope compositions show that the sulfur and ore-forming fluids derived from a deep-seated igneous source. During the peak collisional period between the North China Craton and the Yangtze Craton, the ore-forming fluids that derived from a deep igneous source extracted base and precious metals and flowed upwards through the channels that formed during tectonism. Fluid immiscibility and volatile exsolution led to the crystallization of molybdenite and other minerals, and the formation of economic orebodies in the Qianfanling Mo deposit.     

The Trace Element Distribution Patterns of Ediacaran-Early Cambrian Black Shales and the Origin of Selenium in the Guangning Area, Western Guangdong Province, South China

The Ediacaran and early Cambrian black shales are widespread across the South China Craton (Yangtze and Cathaysia blocks). However, the trace element distribution patterns of the Ediacaran and early Cambrian black shales in the Cathaysia Block are still unclear. In this study, thirty-four black shale samples in the Lechangxia Group (Ediacaran) and thirteen black shale samples in the lower Bacun Group (early Cambrian) from Guangning area, western Guangdong Province, South China, were analyzed for major and trace elements concentrations. Compared to the upper continental crust, the Ediacaran black shales exhibit strongly enriched Se, Ga, and As with enrichment factor values (EF) higher than 10, significantly enriched Bi and Rb (10>EF>5), weakly enriched Mo, Ba, Cs, V, In, Be, Tl, and Th (5>EF>2), normal U, Cr, Cd, Sc, Pb, Cu, and Li (2>EF>0.5), and depleted Ni, Zn, Sr, and Co. Early Cambrian black shales display strongly enriched Se, Ga, and As, significantly enriched Ba, Bi, and Rb, weakly enriched Mo, Cs, Cd, V, U, Be, In, and Tl, normal Sc, Th, Cr, Li, Cu, Ni, and Pb and depleted Co, Zn, and Sr. Moreover, Se is the most enriched trace element in the Ediacaran and early Cambrian black shales: concentrations vary from 0.25 to 30.09 ppm and 0.54 to 5.01 ppm, and averaging 4.84 and 1.72 ppm, with average EF values of 96.87 and 34.32, for the Ediacaran and early Cambrian shales respectively. The average concentration of Se in the Ediacaran black shales is 2.8 times higher than that of early Cambrian black shales. Se contents in the Ediacaran and early Cambrian black shales exhibit significant variation (P = 0.03). Provenance analysis showed that Se contents of both the Ediacaran and early Cambrian black shales were without detrital provenance and volcanoclastic sources, but of hydrothermal origin. The deep sources of Se and the presence of pyrite may explain the higher Se contents in the Ediacaran black shales. Similar with the Se-rich characteristics of the contemporaneous black shales in the south Qingling Mountain and Yangtze block, the Ediacaran and early Cambrian black shales in Guangning area, Cathaysia, are also enriched in Se, which may provide a clue for looking for the selenium-rich resources in western Guangdong Province.     

震旦纪地层黄铁矿硫同位素组成时－空变化特征及扬子地块与晚元古超大陆关系的论证

 扬子地区早震旦世时期沉积岩黄铁矿具有重的硫同位素组成,其δ¹⁴S值从早震旦世椿木组地层的24‰左右逐渐变得更正。在早震旦世扬子地区广泛沉积碳酸锰矿和黑色页岩的民乐组时期达到极正值+60‰,然后又降低至+16‰-+20‰。上述硫同位素组成的时-空变化特征支持了扬子地块属晚元古Rodinia超大陆的一个组成部分的假设。从晚震旦世早期陡山沱组底部开始,沉积岩中黄铁矿硫同位素的δ¹⁴SS出现负值,并继续降低至-27‰以下。早震旦世晚期-晚震旦世早期沉积岩中硫同位素组成特征反映了沉积盆地古海洋环境的剧烈变化,它与大约7亿年时Rodinia超大陆的解体以及扬子地块与其它大陆分离的地质推测相吻合。     

New insights into the origin of early Cambrian carbonate-hosted Pb-Zn deposits in South China: A case study of the Maliping Pb-Zn deposit

The western margin of the Yangtze Block hosts the giant Upper Yangtze Pb-Zn metallogenic province, with the occurrence of >400 carbonate-hosted Pb-Zn deposits. More than 50% of these deposits are hosted in carbonate rocks of late Ediacaran to early Cambrian age. Although they have attracted great attention over the past two decades, it is still unclear why such carbonate sequences host so many Pb-Zn deposits and the role that the country rocks played during mineralization. The newly-discovered Maliping Pb-Zn deposit (~6 Mt @ 4.18 wt% Pb and 9.18 wt% Zn) is hosted in early Cambrian strata composed of carbonate and phosphate rocks, black shales, as well as evaporite sulfates, of which the carbonate rocks are the direct ore-hosting rocks. Evidence from mineralogy and the concentrations of ore-forming metals indicate that the phosphate rocks played an important role in providing geochemical barriers during Pb-Zn ore formation. Homogenization temperatures of the primary fluid inclusions in sphalerite and quartz range from 185 to 282 °C, and their salinities vary from 3.39 to 17.17 wt% NaCl equiv. The REE and C-O isotopes imply that the hydrothermal carbonates were formed under relatively oxidizing conditions and that the wall rocks were involved in the Pb-Zn mineralization through dissolution. Sulfur isotopic compositions (δ³⁴S = +7.60–+31.79‰) of sulfides reveal that S²⁻ originated from evaporite sulfates within the ore-hosting strata, and that the black shales acted as an important reducing agent during thermo-chemical reduction (TSR). Pb isotopic ratios of galena (²⁰⁶Pb/²⁰⁴Pb = 17.856–17.973, ²⁰⁷Pb/²⁰⁴Pb = 15.668–15.689 and ²⁰⁸Pb/²⁰⁴Pb = 37.953–38.101) are similar to those of Proterozoic basement rocks in the region. This implies that the basement could be the key source of mineralizing metals. Hence, we propose that: (i) The favorable lithological combination of early Cambrian phosphate rocks, black shales, carbonates and evaporites, as well as Proterozoic basement in the area, were responsible for controlling the majority of Pb-Zn deposits in the late Ediacaran-early Cambrian carbonate sequences in the western Yangtze Block; and (ii) the Maliping Pb-Zn deposit resulted from a combination of mineralized fluids, various trap structures and favorable lithologies, of which the fluids were epigenetic with low to moderate temperatures and salinities.     

Pb-Pb dating of black shales from the Lower Cambrian and Neoproterozoic strata, South China

Black shales occur widely in the Lower Cambrian and Neoproterozoic strata on the Yangtze Platform, South China. In this study, Lower Cambrian black shales from Xiuning section and Late Neoproterozoic black shales from Weng’an section were studied and Pb isotopic compositions were analyzed following a stepwise acid-leaching technique. The ²⁰⁶Pb/²⁰⁴Pb ratios in both sections show large variations, from 18.906 to 43.737 in the Weng’an section and from 24.811 to 38.110 in the Xiuning section. In contrast, the ranges for ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb values in both sections are relatively smaller from 15.649 to 17.126 and 37.744-38.199 in the Weng’an section, and from 16.034 to 16.783 and 38.602-39.391 in the Xiuning section, respectively. These data yielded two Pb isotope isochron ages of 536±39 and 572±36 Ma, respectively. These ages well accord with other published data and we suggest that they represent the depositional ages for the Lower Cambrian Hetang Formation and the upper Neoproterozoic Doushantuo Formation in South China.     

Paleoceanographic Indicators for Early Cambrian Black Shales from the Yangtze Platform,South China: Evidence from Biomarkers and Carbon Isotopes

The lower Cambrian Niutitang Formation, a widespread black shale deposition, is of geological interest because of its polymetallic beds, Cambrian explosion, depositional ages, dramatic environmental changes and so on. Previous study focused mainly on inorganic geochemistry and few studies have investigated the organic fractions of upper Neoproterozoic-lower Cambrian strata in South China. Here we report a study of biomarkers plus organic carbon isotopes for black shales from Ganziping, Hunan Province (China). All the saturated hydrocarbon fractions have a unimodal distribution of n-alkanes, a high content of short-chain alkanes and maximize at C 19 or C 20 (C 23 for sample Gzh00-1). The C 27 /C 29 sterane ratio ranges from 0.77 to 1.20 and 4-methylsteranes are in low abundance. These parameters indicate that algae and bacteria are the important primary producers. Furthermore, biomarker maturity proxies show the samples to be higher maturity. The low Pr/Ph values (<0.7) suggest that the samples were deposited under anoxic conditions and, likely, under stratified water columns. In addition, 25-norhopanes and gammacerane are present as diagnostic indicators of normal marine salinity and dysoxic to anoxic conditions. During the Early Tommotian, known to coincide with a transgression event, small shelly fossils increased in abundance and diversity. Moreover, positive δ 13 C org excursions close to 1.4‰ occur at the base of the Tommotian stage. In summary, the Early Cambrian black shales were deposited under dramatic paleoenvironmental changes, including oceanic anoxia, higher primary productivity and sea-level rise.     

Microcrystalline dolomite in a middle Permian volcanic lake: Insights on primary dolomite formation in a non-evaporitic environment

Lacustrine dolomite nucleation commonly occurs in modern and Neogene evaporitic alkaline lakes. As a result, ancient lacustrine microcrystalline dolomite has been conventionally interpreted to be formed in evaporitic environments. This study, however, suggests a non-evaporitic origin of dolomite precipitated in a volcanic–hydrothermal lake, where hydrothermal and volcanic processes interacted. The dolomite occurs in lacustrine fine-grained sedimentary rocks in the middle Permian Lucaogou Formation in the Santanghu intracontinental rift basin, north-west China. Dolostones are composed mainly of nano-sized to micron-sized dolomite with a euhedral to subhedral shape and a low degree of cation ordering, and are interlaminated and intercalated with tuffaceous shale. Non-dolomite minerals, including quartz, alkaline feldspars, smectite and magnesite mix with the dolomite in various proportions. The ⁸⁷Sr/⁸⁶Sr ratios (0.704528 to 0.705372, average = 0.705004) and δ²⁶Mg values (−0.89 to −0.24‰, average = −0.55‰) of dolostones are similar to those of mantle rocks, indicating that the precipitates mainly originated from fluids that migrated upward from the mantle and were subject to water–rock reactions at a great depth. The δ¹⁸O values (−3.1 to −22.7‰, average = −14.0‰) of the dolostones indicate hydrothermal influence. The trace and rare earth element concentrations suggest a saline, anoxic and volcanic–hydrothermally-influenced subaqueous environment. In this subaqueous environment of Lucaogou lake, locally high temperatures and a supply of abundant Mg²⁺ from a deep source induced by volcanic–hydrothermal activity formed favourable chemical conditions for direct precipitation of primary dolomite. This study's findings deepen the understanding of the origin and processes of lacustrine primary dolomite formation and provide an alternative possibility for environmental interpretations of ancient dolostones.     

Large Zn isotope variations in the NiMo polymetallic sulfide layer in the lower Cambrian,South China

In South China, black organic-rich shales in the lower Cambrian Niutitang Formation host a NiMo polymetallic sulfide layer that discontinuously extends over ~1600 km. Seawater and hydrothermal origins are among the many suggested hypotheses and are still under debate. In order to discriminate Zn sources, we report Zn isotopes in NiMo polymetallic sulfide layers and their host shales from the Nayong and Zunyi locations in Guizhou province and the Zhangjiajie section in Hunan province. In each section, host organic-rich shales show homogeneous Zn isotope compositions which likely resulted from quantitative scavenging of dissolved Zn from seawater under euxinic conditions. The difference in the average δ⁶⁶Zn values of organic-rich shales between the two sections in Guizhou (0.76 ± 0.09‰) and one section in Hunan (0.59 ± 0.10‰) might reflect variations of Zn isotope gradient with the depth of seawater. Therefore, the organic-rich sediments need not always represent an isotopically light Zn sink, which is dependent on Zn isotope fractionation in the local basin. However, the δ⁶⁶Zn values in the NiMo polymetallic sulfide layers are different from those of their host shales, indicating that these sulfide layers did not inherit the Zn isotope signal of seawater. Based on the regular increasing trend in δ⁶⁶Zn values from Nayong (0.54 ± 0.06‰) to Zhangjiajie (1.34 ± 0.09‰) and the presence of PbZn mineralization in the Dengying/Doushantuo Formations, we argue that hydrothermal fluids associated with PbZn mineralization could be a major source of Zn in NiMo sulfide layers, especially in the Nayong location. A possible model is that the hydrothermal fluids related to MVT-type mineralization got overprinted on a multiple-sourced synsedimentary sulfide-rich layer. We provide additional evidence that Zn isotopes have great potential as a tracer of metal source and can be applied to similar types of mineralization as e.g., the late Devonian Ni-Zn-PGE Nick deposit (Selwyn Basin, Canada) or elsewhere.     

Application of sulfur and carbon isotopes to oil–source rock correlation: A case study from the Tazhong area,Tarim Basin,China

Up until now, it has been assumed that oil in the Palaeozoic reservoirs of the Tazhong Uplift was derived from Upper Ordovician source rocks. Oils recently produced from the Middle and Lower Cambrian in wells ZS1 and ZS5 provide clues concerning the source rocks of the oils in the Tazhong Uplift, Tarim Basin, China. For this study, molecular composition, bulk and individual n-alkane δ¹³C and individual alkyl-dibenzothiophene δ³⁴S values were determined for the potential source rocks and for oils from Cambrian and Ordovician reservoirs to determine the sources of the oils and to address whether δ¹³C and δ³⁴S values can be used effectively for oil–source rock correlation purposes. The ZS1 and ZS5 Cambrian oils, and six other oils from Ordovician reservoirs, were not significantly altered by TSR. The ZS1 oils and most of the other oils, have a “V” shape in the distribution of C₂₇–C₂₉ steranes, bulk and individual n-alkane δ¹³C values predominantly between −31‰ to −35‰ VPDB, and bulk and individual alkyldibenzothiophene δ³⁴S values between 15‰ to 23‰ VCDT. These characteristics are similar to those for some Cambrian source rocks with kerogen δ¹³C values between −34.1‰ and −35.3‰ and δ³⁴S values between 10.4‰ and 21.6‰. The oil produced from the Lower Ordovician in well YM2 has similar features to the ZS1 Cambrian oils. These new lines of evidence indicate that most of the oils in the Tazhong Uplift, contrary to previous interpretations, were probably derived from the Cambrian source rocks, and not from the Upper Ordovician. Conversely, the δ¹³C and δ³⁴S values of ZS1C Cambrian oils have been shown to shift to more positive values due to thermochemical sulfate reduction (TSR). Thus, δ¹³C and δ³⁴S values can be used as effective tools to demonstrate oil–source rock correlation, but only because there has been little or no TSR in this part of the section.     

湖北宜昌地区寒武系—下奥陶统的碳氧同位素记录

对宜昌地区寒武系和下奥陶统的碳酸盐碳、氧同位素进行测定,所得δ18O大 于－10‰且与δ13C不相关,表明研究区碳酸盐样品基本上保存了碳、氧同位素的初 始比值。δ18O在白云岩样品中呈现正漂移而在非白云岩样品中呈现负漂移,认为δ 18O反映海水古盐度变化,即δ18O随着古盐度升高而增大;δ13 C在缺氧沉积物中呈现负漂移,但负漂移的δ13C却不限于缺氧沉积物,推测δ13 C可能反映古海洋的初级生产力,即δ13C随着初级生产力的提高而降低。研究还指 出,由于Z值与δ13C密切正相关（相关系数为0.99）,综合运用δ18O和δ 13C的经典盐度公式不适用于研究区古盐度环境的重建。     

峡东地区寒武系岩石学、沉积学特征及储集性

研究区位于扬子板块中段,地层发育齐全,构造层次清晰,交通方便(图1),因此早在本世纪初就有不少地质学家涉足此地(李四光、赵亚曾,1924)。该区地质研究程度较高,尤其在古生物地层学研究方面成果甚丰,其中前寒武系和寒武系的界线剖面已被国际地科联确定为该界线层型的主要参考点;寒武系和奥陶系亦被确定为我国南方寒武系、奥陶系的主要标准剖面;奥陶系与志留系界线剖面正在争取成为国际层型剖面。寒武系的研究有     

Hydrothermal venting activities in the Early Cambrian,South China: Petrological,geochronological and stable isotopic constraints

Multi-episodic (three episodes at least) hydrothermal silica chimneys are identified in the black chert successions (up to ～ 100 m thick locally), overlain by thick black shales (up to a few 100 m thick), in the Ediacaran–Cambrian boundary successions along the southern marginal zone of the Yangtze Platform, South China. Their occurrences are constrained within the lowermost Cambrian by the SHRIMP U–Pb zircon dating and stable isotopic chemostratigaphic data, and are stratigraphically coincident with the negative isotopic excursions of organic carbon (～ 10‰ VPDB in magnitude) and sulfide sulfur (between 0 and 10‰ CDT), i.e., in bases of Nemakit–Daldynian and Tommotian stages in the Lower Cambrian. In this case, a causal link could have existed between which the hydrothermal venting could have released huge amounts of reduced silica-rich hydrothermal fluids with abundant ¹³C-depleted greenhouse gases (methane) and volcanic-originated H₂S into the ocean and/or atmosphere, resulting in an extreme warm climate and oceanic anoxia, oceanic chemical perturbation, and subsequent massive precipitation of silica (chert), and large-magnitude negative isotopic excursions of organic carbon and sulfide sulfur. This scenario provides a unique chance to explore the causes of apparent tectono-depositional, oceanic and geochemical perturbations during this critical interval in South China and elsewhere.     

A pronounced negative δ13C excursion in an Ediacaran succession of western Yangtze Platform: A possible equivalent to the Shuram event and its implication for chemostratigraphic correlation in South China

A pronounced negative δ¹³C shift that can be potentially correlated with the Shuram excursion has been reported from middle Ediacaran strata in the Yangtze Gorges area of South China. Whether it represents a perturbation to the ocean carbon cycle or a record of post-depositional alteration is still open to debate. Resolving this controversy will help clarify if δ¹³C variations can be used for chemostratigraphic correlation of Ediacaran successions. To further understand the regional pattern of Ediacaran carbon isotopic excursions in the Yangtze platform, we carried out a detailed δ¹³C analysis of the Lianghong section in the western part of the Yangtze platform. The Ediacaran System at Lianghong is overlain by the Maidiping Formation yielding early Cambrian small shelly fossils and underlain by the Cryogenian Lieguliu Formation diamictite and tuffaceous siltstones. It comprises the Guanyinya and Hongchunping formations, which have been traditionally correlated with the Doushantuo and Dengying formations, respectively, in the Yangtze Gorges area. Two negative δ¹³C excursions occur in the Lianghong section. The lower one at the uppermost Guanyinya Formation, with a nadir at − 8.6‰, may be correlated with the pronounced negative δ¹³C shift (EN3) in the uppermost Doushantuo Formation in the Yangtze Gorges area and possibly with the well known Shuram event in Oman. The upper negative δ¹³C excursion occurs in the upper Hongchunping Formation and may be correlated with negative excursions (EN4) near the Ediacaran/Cambrian boundary. Other negative δ¹³C excursions (e.g., EN1 and EN2) are not expressed in the Lianghong section because the lower Guanyinya Formation is dominated by siliciclastic rocks. Combined with previously published Ediacaran δ¹³C profiles, our results indicate that the EN3 excursion (likely a Shuram equivalent) may occur widely in South China and can be a useful chemostratigraphic feature for regional and global stratigraphic correlation.     

Molybdenum Mass Fractions and Stable Isotope Compositions of Sedimentary Carbonate and Silicate Reference Materials

A double‐spike method in combination with MC‐ICP‐MS was applied to obtain molybdenum (Mo) mass fractions and stable isotope compositions in a suite of sedimentary silicate (marine, lake, stream, estuarine, organic‐rich sediment, shales, slate, chert) and carbonate reference materials (coral, dolomite, limestones, carbonatites), and a manganese nodule reference material, poorly characterised for stable Mo isotope compositions. The Mo contents vary between 0.076 and 364 μg g^?1, with low‐Mo mass fractions (< 0.29 μg g^?1) found almost exclusively in carbonates. Intermediate Mo contents (0.73–2.70 μg g^?1) are reported for silicate sediments, with the exception of chert JCh‐1 (0.24 μg g^?1), organic‐rich shale SGR‐1b (36.6 μg g^?1) and manganese nodule NOD‐A‐1 (364 μg g^?1). The Mo isotope compositions (reported as δ⁹⁸Mo relative to NIST SRM 3134) range from ?1.77 to 1.03‰, with the intermediate precision varying between ± 0.01 and ± 0.12‰ (2s) for most materials. Low‐temperature carbonates show δ⁹⁸Mo values ranging from 0.21 to 1.03‰ whereas δ⁹⁸Mo values of ?1.77 and ?0.17‰ were obtained for carbonatites CMP‐1 and COQ‐1, respectively. Silicate materials have δ⁹⁸Mo values varying from ?1.56 to 0.73‰. The range of δ⁹⁸Mo values in reference materials may thus reflect the increasingly important relevance of Mo isotope investigations in the fields of palaeoceanography, weathering, sedimentation and provenance, as well as the magmatic realm.     

Nitrogen isotope chemostratigraphy of the Ediacaran and Early Cambrian platform sequence at Three Gorges,South China

The appearance of multicellular animals and subsequent radiation during the Ediacaran/Cambrian transition may have significantly changed the oceanic ecosystem. Nitrogen cycling is essential for primary productivity and thus its connection to animal evolution is important for understanding the co-evolution of the Earth's environment and life. Here, we first report on coupled organic carbon and nitrogen isotope chemostratigraphy from the entire Ediacaran to Early Cambrian period by using drill core samples from the Yangtze Platform, South China. The results show that δ¹⁵N_TN values were high (~ + 6‰) until middle Ediacaran, gradually dropping down to − 1‰ at the earliest Cambrian, then rising back to + 4‰ in the end of the Early Cambrian. Organic carbon and nitrogen contents widely varied with a relatively constant C/N ratio in each stratigraphic unit, and do not apparently control the carbon and nitrogen isotopic trends. These observations suggest that the δ¹⁵N_TN and C/N trends mainly reflect secular changes in nitrogen cycling in the Yangtze Platform. Onset of the observed negative N isotope excursion coincided with a global carbon isotope excursion event (Shuram excursion). Before the Shuram event, the high δ¹⁵N probably reflects denitrification in a nitrate-limited oceanic condition. Also, degradation of dissolved and particulate organic matter could be an additional mechanism for the ¹⁵N-enrichment, and may have been significant when the ocean was rich in organic matter. At the time of the Shuram event, both δ¹³C_carb and δ¹⁵N_TN values were dropped probably due to massive re-mineralization of organic matter. This scenario is supported by an anomalously low C/N ratio, implying that enhanced respiration resulted in selective loss of carbon as CO₂ with recycled organic nitrogen. After the Shuram event, the δ¹⁵N value continued to decrease despite that δ¹³C_carb rose back to + 4‰. The continued δ¹⁵N drop appears to have coincided with a decreasing phosphorus content in carbonate. This suggests that ocean oxygenation may have generated a more nitrate-rich condition with respect to phosphorus as a limiting nutrient. Similar to the Shuram event, another negative δ¹³C_carb event in the Canglanpuan stage of the Early Cambrian is also characterized by carbon isotopic decoupling as well as the low C/N ratio. The results strongly support that the two stages of the decoupled negative δ¹³C_carb excursions reflect a disappearance of a large organic carbon pool in the ocean. The two events appear to relate with the appearance of new metazoan taxa with novel feeding strategies, suggesting a link between ocean oxygenation, nutrient cycling and the appearance and adaptation of metazoans. The nitrogen isotope geochemistry is very useful to understand the link between the environmental, ecological and biological evolutions.